CN108682883B - Hydrogen bond self-crosslinking sulfonated polyimide membrane and preparation method and application thereof - Google Patents
Hydrogen bond self-crosslinking sulfonated polyimide membrane and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a hydrogen bond self-crosslinking sulfonated polyimide membrane, which comprises a non-amino-terminated sulfonated polyimide high molecular polymer and an amino-terminated sulfonated polyimide high molecular polymer, wherein the non-amino-terminated sulfonated polyimide high molecular polymer and the amino-terminated sulfonated polyimide high molecular polymer are crosslinked through hydrogen bonds, and the mass ratio of the non-amino-terminated sulfonated polyimide high molecular polymer to the amino-terminated sulfonated polyimide high molecular polymer is 1: 0.25 to 4. The invention also correspondingly provides a preparation method of the film. The hydrogen bond self-crosslinking sulfonated polyimide membrane not only has excellent ion exchange capacity, but also has excellent vanadium and proton selection resistance. The diaphragm prepared by the method is applied to the all-vanadium redox flow battery, can effectively improve the efficiency of the battery, and has good application prospect.
Description
Technical Field
The invention belongs to the field of battery diaphragms, and particularly relates to a sulfonated polyimide membrane and a preparation method and application thereof.
Background
Pollution caused by the massive use of non-renewable resources by human beings has become a main source of air pollution, and therefore, the utilization of renewable energy has been highly regarded by countries in the world. However, the renewable energy power generation process has obvious discontinuity and instability, and is easily influenced by factors such as power generation time, day and night, seasons and the like. The efficient energy storage device is an important means for solving the unstable state characteristic of the renewable energy power generation. The all-vanadium redox flow battery is a novel green battery, has the characteristics of adjustable capacity and power, large-current lossless deep discharge, safe operation, easy operation and maintenance, long service life, no environmental pollution and the like, and can be applied to various fields of energy storage equipment of renewable energy sources, emergency power supply systems, peak regulation and frequency modulation of power grids and the like.
The performance of the diaphragm, which is one of the key materials of the all-vanadium flow battery, directly affects the performance, the service life and the cost of the battery. The ideal separator material must have the following characteristics: (1) the material has excellent chemical stability under strong acid and strong oxidizing environment; (2) has good ion selectivity, i.e., low vanadium ion permeability and high ion conductivity, thereby improving the efficiency of the battery; (3) the mechanical property is good; (4) has lower cost. The physical and chemical properties of the separator (e.g. ion conductivity, vanadium resistance, chemical stability and mechanical strength, etc.) and the cost therefore directly determine the efficiency, operating life and technical economy of the battery.
At present, perfluorosulfonic acid (Nafion) series membranes which are produced by DuPont in the United states and have good chemical stability and high proton conductivity are applied to all-vanadium flow batteries. However, Nafion series membranes have some of the following disadvantages: (1) high vanadium ion permeation reduces the efficiency of the cell; (2) the high water migration enables the two-pole liquid of the battery to be easily and rapidly unbalanced, and the service life of the battery is shortened; (3) the expensive price makes the cost of the whole cell too high for large-scale commercial application. Therefore, a great deal of research work on the diaphragm material for the all-vanadium redox flow battery is carried out at home and abroad. Among them, the sulfonated polyimide film is considered to be one of the important candidates for the diaphragm material for the all-vanadium redox flow battery due to its advantages of good film forming property, excellent vanadium resistance, excellent proton selectivity, low price, etc. However, sulfonated polyimide membranes have inferior chemical stability and poor proton conductivity, which greatly reduces the service life of the battery.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects and defects mentioned in the background technology, provide a hydrogen bond self-crosslinking sulfonated polyimide membrane with high chemical stability and proton conductivity, and correspondingly provide a preparation method and application thereof. In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a hydrogen bond self-crosslinking sulfonated polyimide membrane comprises a non-amino-terminated sulfonated polyimide high molecular polymer and an amino-terminated sulfonated polyimide high molecular polymer, wherein the non-amino-terminated sulfonated polyimide high molecular polymer and the amino-terminated sulfonated polyimide high molecular polymer are crosslinked through hydrogen bonds, and the mass ratio of the non-amino-terminated sulfonated polyimide high molecular polymer to the amino-terminated sulfonated polyimide high molecular polymer is 1: 0.25 to 4. The obtained hydrogen bond self-crosslinking sulfonated polyimide film has better and excellent comprehensive performance in the mass ratio.
In the above-mentioned hydrogen bond self-crosslinking sulfonated polyimide film, preferably, the non-amino-terminated sulfonated polyimide high-molecular polymer and the amino-terminated sulfonated polyimide high-molecular polymer are randomly crosslinked by a hydrogen bond.
In the above-mentioned hydrogen bond self-crosslinking sulfonated polyimide film, preferably, the thickness of the hydrogen bond self-crosslinking sulfonated polyimide film is 30 to 65 μm. The thickness is one of the important indexes of the diaphragm, and the thickness directly influences the mass transfer performance and vanadium resistance performance of the diaphragm in the all-vanadium redox flow battery. The excessive thickness is not favorable for the transfer of protons and can increase the cost; too thin a thickness causes a problem of severe vanadium infiltration.
In the above-mentioned hydrogen bond self-crosslinking sulfonated polyimide film, preferably, the chemical structural formula of the hydrogen bond self-crosslinking sulfonated polyimide film is as follows:
in the above-mentioned hydrogen bond self-crosslinking sulfonated polyimide film, preferably, the chemical structural formula of the non-amino-terminated sulfonated polyimide high molecular polymer is as follows:
the chemical structural formula of the amino-terminated sulfonated polyimide high-molecular polymer is as follows:
the chemical reaction process of the non-amino-terminated sulfonated polyimide high molecular polymer and the amino-terminated sulfonated polyimide high molecular polymer through hydrogen bond crosslinking is as follows:
as a general technical concept, the present invention also provides a method for preparing the above-mentioned hydrogen bond self-crosslinking sulfonated polyimide membrane, comprising the steps of:
(1) preparing non-amino-terminated sulfonated polyimide high molecular polymer and amino-terminated sulfonated polyimide high molecular polymer by a high-temperature polycondensation method;
(2) dissolving the non-amino-terminated sulfonated polyimide high molecular polymer prepared in the step (1) and the amino-terminated sulfonated polyimide high molecular polymer in an organic solvent to prepare a high molecular polymer solution, mixing and stirring uniformly, casting to form a film, and drying, soaking and washing to prepare the hydrogen bond self-crosslinking sulfonated polyimide film.
In the preparation method, in the step (1), the high-temperature polycondensation method is preferably a dehydration polycondensation reaction of a diamine monomer and a dianhydride monomer, and the diamine monomer and the dianhydride monomer used in the preparation of the non-amino-terminated sulfonated polyimide high molecular polymer and the amino-terminated sulfonated polyimide high molecular polymer are the same. The two sulfonated polyimide high molecular polymers are polymerized by the same monomer, have very similar molecular structures and can increase the compatibility of the two sulfonated polyimide high molecular polymers, so that the high molecular casting solution has excellent film forming performance, and the diaphragm consisting of five elements of carbon, hydrogen, nitrogen, oxygen and sulfur is prepared.
In the above preparation method, preferably, the diamine monomer is 2,2 '-disulfonic acid benzidine and 4,4' -diaminodiphenyl ether, and the dianhydride monomer is 1,4,5, 8-naphthalene tetracarboxylic dianhydride; the specific process of the dehydration polycondensation reaction comprises the following steps: (a) mixing and stirring 2,2 '-disulfonic acid benzidine, m-methylphenol and triethylamine in nitrogen or argon gas for dissolving, adding 4,4' -diamino diphenyl ether solid for dissolving, adding 1,4,5, 8-naphthalene tetracarboxylic dianhydride and benzoic acid, heating to 70-100 ℃, reacting for 2-6 h, heating to 160-200 ℃, and reacting for 10-30 h; (b) and (2) cooling the reaction system to below 90 ℃, adding a diluent, continuously stirring, when the temperature of the reaction system is reduced to 50 ℃, pouring the viscous solution obtained after the reaction into a precipitator to generate a precipitate product, filtering, washing the obtained solid with a detergent for 3-5 times, and drying in vacuum at 60-120 ℃ for 10-30 hours to obtain the sulfonated polyimide high molecular polymer.
In the preparation method, in the synthesis process of two sulfonated polyimide high molecular polymers, the step (1) is reacted for 2-6 hours at 70-100 ℃ to open an anhydride five-membered ring of 1,4,5, 8-naphthalene tetracarboxylic dianhydride to form carboxylic acid; the reaction is carried out at 160-200 ℃ for 10-30 h to dehydrate the polymer chain to form an imide ring. Benzoic acid is used as a catalyst for dehydration condensation reaction; triethylamine is used as a cosolvent of 2,2' -disulfonic acid benzidine and a protective agent of a sulfonic acid group; the m-methylphenol is used as a solvent to completely dissolve all the monomer materials to be polymerized.
In the above preparation method, preferably, in the step (a), the molar ratio of the 1,4,5, 8-naphthalene tetracarboxylic dianhydride, 2 '-disulfonic acid dianiline, 4' -diaminodiphenyl ether, and benzoic acid is (1.0 to 16.0): (0.5-8.0): (0.6-10.0): (2.1 to 34.0); the volume ratio of the m-methylphenol to the triethylamine is (7.0-110.0): (0.16-5.2); in the step (b), the diluent is m-methylphenol, the precipitant is any one of acetone, methanol, ethanol or isopropanol, and the detergent is any one of acetone, methanol, ethanol or isopropanol; the volume ratio of the m-methylphenol and the triethylamine serving as the diluents is (1.2-20.0): (0.16-5.2); the volume ratio of the precipitant to the viscous solution is (1.0-10.0): 1.0.
in the above production method, more preferably, in producing the non-amino terminated sulfonated polyimide polymer, the molar ratio of 2,2 '-disulfonic acid benzidine, 4' -diaminodiphenyl ether, and 1,4,5, 8-naphthalene tetracarboxylic dianhydride is 1.0: 1.0: 2.0; when the amino-terminated sulfonated polyimide high molecular polymer is prepared, the molar ratio of 2,2 '-disulfonic acid benzidine, 4' -diaminodiphenyl ether and 1,4,5, 8-naphthalene tetracarboxylic dianhydride is 1.0: 1.25: 2.0. in the preparation process of two sulfonated polyimide high molecular polymers, 2,2 '-disulfonic acid benzidine and 4,4' -diaminodiphenyl ether are used as diamine monomers to carry out dehydration polycondensation reaction with 1,4,5, 8-naphthalene tetracarboxylic dianhydride monomers. Wherein, the sum of the molar weights of the diamines in the non-amino-terminated sulfonated polyimide high molecular polymer is equal to the molar weight of the dianhydride, namely, the optimal molar ratio of the 2,2 '-disulfonic acid benzidine, the 4,4' -diaminodiphenyl ether and the 1,4,5, 8-naphthalene tetracarboxylic dianhydride is 1.0: 1.0: 2.0. the sum of the molar weights of the diamines in the amino-terminated sulfonated polyimide high-molecular polymer is greater than that of the dianhydride, i.e., the optimal molar ratio of 2,2 '-disulfonic acid benzidine, 4' -diaminodiphenyl ether and 1,4,5, 8-naphthalene tetracarboxylic dianhydride is 1.0: 1.25: 2.0. further, benzoic acid is used as a catalyst for the dehydration condensation reaction, and the molar amount thereof is more preferably the sum of the molar amounts of dianhydride and diamine.
In the above preparation method, preferably, in the step (2), the organic solvent is any one of m-methylphenol, dimethyl sulfoxide, N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide; the concentration of the high molecular polymer solution is 0.05-0.10 g/mL; the time for mixing and stirring uniformly is 12-48 h, the temperature for drying the formed film is 50-100 ℃, the drying time is 20-60 h, the soaking is carried out for 20-36 h by using a sulfuric acid aqueous solution with the concentration of 1.0-3.0 mol/L, and the washing is carried out for 3-5 times by using deionized water.
In general, the hydrogen bond self-crosslinking sulfonated polyimide film material obtained by the preparation method has the following bright points: (1) the two sulfonated polyimide high molecular polymers are obtained by one-step high-temperature polycondensation reaction of the same dianhydride and diamine monomers; (2) the two sulfonated polyimide high molecular polymers have very similar molecular structures, so that the problem of compatibility is effectively solved; and (3) basic amino groups of the amino-terminated sulfonated polyimide high-molecular polymer can form hydrogen bonds with acidic sulfonic acid groups, so that molecular chains of the hydrogen bond self-crosslinking sulfonated polyimide membrane can be crosslinked with each other, and a foundation is laid for improving the physical and chemical properties of the hydrogen bond self-crosslinking sulfonated polyimide membrane.
The invention also provides application of the hydrogen bond self-crosslinking sulfonated polyimide film in the field of all-vanadium flow batteries as a general technical concept, and the hydrogen bond self-crosslinking sulfonated polyimide film is used for a diaphragm of the all-vanadium flow batteries.
The invention prepares two sulfonated polyimide high molecular polymers by regulating and controlling the molar ratio of monomers in the polymerization process of sulfonated polyimide high molecules. In the process of preparing the hydrogen bond self-crosslinking sulfonated polyimide membrane, two sulfonated polyimide high molecular polymers are co-dissolved according to a certain mass ratio. The principle that basic amino-terminated groups can form hydrogen bonds with acidic sulfonic acid groups is utilized, two polymer chains are mutually crosslinked, linear single molecular chains are connected into a net, and finally, the hydrogen bond self-crosslinking sulfonated polyimide film is formed. The specially designed hydrogen bond self-crosslinking sulfonated polyimide film has the advantages of low water absorption rate, good dimensional stability, vanadium resistance, proton conductivity and chemical stability.
Compared with the prior art, the invention has the advantages that:
1. compared with the common sulfonated polyimide membrane, the hydrogen bond self-crosslinking sulfonated polyimide membrane has the advantages of low water absorption rate, good dimensional stability and vanadium resistance, and also has excellent ion exchange capacity, proton conductivity and chemical stability.
2. The preparation method has simple process and easy operation, and in the preparation process, the basic amino group of the amino-terminated sulfonated polyimide high molecular polymer can form a hydrogen bond with an acidic sulfonic acid group, so that the molecular chains of the hydrogen bond self-crosslinking sulfonated polyimide membrane can be crosslinked with each other, and the foundation is laid for improving the physical and chemical properties of the hydrogen bond self-crosslinking sulfonated polyimide membrane.
3. The hydrogen bond self-crosslinking sulfonated polyimide membrane can be applied to the all-vanadium redox flow battery, has good application prospect in the field of all-vanadium redox flow batteries, and can enable the battery to show excellent efficiency.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is an infrared spectrum of a hydrogen bond self-crosslinking sulfonated polyimide film prepared in example 1.
FIG. 2 is a NMR spectrum of the hydrogen bond self-crosslinking sulfonated polyimide film prepared in example 1.
Fig. 3 is a scanning electron microscope image of the surface and cross section of the hydrogen bond self-crosslinking sulfonated polyimide membrane prepared in example 1 at different magnifications.
Fig. 4 is a sectional elemental analysis diagram of the hydrogen bond self-crosslinking sulfonated polyimide film prepared in example 1.
Fig. 5 is a graph comparing the vanadium ion permeation rates of the hydrogen bond self-crosslinking sulfonated polyimide membrane prepared in example 1 and a commercial Nafion115 membrane.
Fig. 6 is a graph comparing the efficiency of all vanadium flow batteries using hydrogen bonding self-crosslinking sulfonated polyimide membranes prepared in example 1 and commercial Nafion115 membranes.
Detailed Description
In order to facilitate an understanding of the invention, the invention will be described more fully and in detail below with reference to the accompanying drawings and preferred embodiments, but the scope of the invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1:
a hydrogen bond self-crosslinking sulfonated polyimide membrane is 50 mu m thick and is prepared from a non-amino-terminated sulfonated polyimide high molecular polymer and an amino-terminated sulfonated polyimide high molecular polymer according to a mass ratio of 1.0: 1.0 are obtained by hydrogen bond crosslinking.
The preparation method of the hydrogen bond self-crosslinking sulfonated polyimide membrane comprises the following steps:
(1) under the protection of argon, 4.0mmol of 2,2' -disulfonic acid benzidine, 55.0mL of m-methylphenol and 2.6mL of triethylamine are put into a 250mL three-neck round-bottom flask with a serpentine condenser tube and stirred until solid is dissolved; then 4.0mmol of 4,4' -diaminodiphenyl ether is added, and the mixture is stirred until the solid is dissolved; finally, 8.0mmol of 1,4,5, 8-naphthalene tetracarboxylic dianhydride and 16.0mmol of benzoic acid are added, the stirring temperature is increased to 80 ℃, the reaction is carried out for 4.5h at the temperature, the temperature is increased to 180 ℃, and the reaction is carried out for 20 h; cooling the reaction system to below 90 ℃, adding 10.0mL of m-methylphenol, stirring the whole reaction process, when the temperature of the reaction system is reduced to 50 ℃, pouring the viscous solution obtained after the reaction into 300mL of acetone serving as a precipitator (the volume ratio of the precipitator to the viscous solution is 4.6: 1.0), generating a precipitation product, filtering, washing the obtained solid with acetone for 3 times, and then carrying out vacuum drying at 80 ℃ for 24 hours to obtain the non-amino-terminated sulfonated polyimide high molecular polymer;
(2) the preparation process of the amino-terminated sulfonated polyimide high-molecular polymer is consistent with the step (1); but the adding amount of the 4,4' -diaminodiphenyl ether is 5.0mmol, and the adding amount of the benzoic acid is 17.0 mmol;
(3) mixing the non-amino-terminated sulfonated polyimide high molecular polymer and the amino-terminated sulfonated polyimide high molecular polymer prepared in the steps (1) and (2) according to the weight ratio of 1.0: dissolving the mixture in m-methylphenol according to the mass ratio of 1.0 to prepare a high molecular polymer solution with the concentration of 0.08g/mL, and stirring the polymer solution for 24 hours until the polymer solution is uniform; finally, the polymer solution is cast into a film on a clean, smooth and dry glass plate, the thickness of the film is controlled to be 50 microns, the film is dried for 24 hours at the temperature of 60 ℃, the diaphragm is stripped from the glass plate and then is placed into 1.0mol/L sulfuric acid aqueous solution to be soaked for 24 hours, then the diaphragm is taken out, and the diaphragm is repeatedly washed for 3 times by deionized water, so that the hydrogen bond self-crosslinking sulfonated polyimide film in the embodiment is prepared.
The physical and chemical properties of the hydrogen bond self-crosslinking sulfonated polyimide membrane obtained in this example are shown in table 1.
Table 1: physical and chemical properties of the hydrogen bond self-crosslinking type sulfonated polyimide film prepared in example 1
As can be seen from Table 1, the ion exchange capacity of the sulfonated polyimide membrane of the hydrogen bond self-crosslinking type in this example is 2.7 times that of the commercial Nafion115 membrane (0.74meq/g), which is beneficial for obtaining more proton conduction sites; due to the interaction force of the hydrogen bonds between the basic amino-terminated group and the acidic sulfonic acid group, the water absorption rate and the swelling rate of the hydrogen bond self-crosslinking sulfonated polyimide membrane are reduced compared with those of the traditional linear sulfonated polyimide membrane, and the improvement on the dimensional stability and the mechanical property of the hydrogen bond self-crosslinking sulfonated polyimide membrane is facilitated; the proton selectivity of the hydrogen bond self-crosslinking sulfonated polyimide membrane is Nafion115 membrane (0.44 multiplied by 10)5S min/cm3) Is twice the proton conductivity of a commercially acceptable value (0.01S/cm), which means that high efficiencies will be obtained for all-vanadium flow batteries using the membrane.
FIG. 1 is an infrared spectrum of a hydrogen bond self-crosslinking type sulfonated polyimide film in this example, which is seen at 1712.2 and 1671.1cm-1Peaks at positions are symmetric and asymmetric stretching vibrations of carbonyl (C ═ O); 1346.3cm-1The vibration peak at (A) is attributed to the C-N-C bond stretching vibration of the imide. The appearance of these peaks indicates that the polycondensation reaction during the preparation of the two sulfonated polyimide high molecular weight polymers proceeds relatively completely. At 1099.5cm-1And 1027.7cm-1The absorption band at (b) is attributed to the stretching vibration of the sulfonic acid group.
In order to further characterize the chemical structure of the hydrogen bond self-crosslinking sulfonated polyimide membrane, the nuclear magnetic resonance hydrogen spectrum test was also performed on the hydrogen bond self-crosslinking sulfonated polyimide membrane in this example, as shown in fig. 2. It is understood from FIG. 2 that the peak at 8.75ppm corresponds to the hydrogen atom (Hd) on the naphthalene ring of the hydrogen bond self-crosslinking sulfonated polyimide membrane; peaks between 7.2 and 8.2ppm were assigned to the hydrogen atoms on the benzene ring of 2,2 '-disulfonic acid benzidine and 4,4' -diaminodiphenyl ether. Wherein peaks at 7.4, 7.8, and 8.1ppm are hydrogen atoms (Ha, Hb, and Hc) at para, ortho, and meta positions of the sulfonic acid group on the benzene ring of 2,2 '-biphenylanilide disulfonate, respectively, and peaks at 7.6 and 7.3ppm correspond to two hydrogen atoms (He and Hf) on the benzene ring of 4,4' -diaminodiphenyl ether, respectively. The signals on the nuclear magnetic resonance hydrogen spectrum can be reasonably attributed to the molecular structural units of the hydrogen bond self-crosslinking sulfonated polyimide membrane.
Fig. 3 is a scanning electron microscope image of the surface and cross section of the hydrogen bond self-crosslinking sulfonated polyimide membrane prepared in this example under different magnifications. Fig. 4 is a sectional elemental analysis diagram of the hydrogen bond self-crosslinking sulfonated polyimide film prepared in this example. As can be seen from fig. 3 and 4, under different magnifications, the hydrogen bond self-crosslinking sulfonated polyimide film in the present embodiment has a dense and uniform micro-morphology on both the surface and the cross section; the elements of the film obtained by elemental analysis include carbon, nitrogen, oxygen, and sulfur. The energy spectrum can not collect the signal of hydrogen element, but the nuclear magnetic resonance hydrogen spectrum proves the existence of hydrogen element in the prepared hydrogen bond self-crosslinking sulfonated polyimide film. Therefore, the hydrogen bond self-crosslinking sulfonated polyimide film is composed of five elements of carbon, nitrogen, hydrogen, oxygen and sulfur.
Fig. 5 is a graph comparing the vanadium ion permeation rates of the hydrogen bond self-crosslinking sulfonated polyimide membrane prepared in this example and a commercial Nafion115 membrane. As can be seen from fig. 5, the hydrogen bond self-crosslinking sulfonated polyimide membrane of the present example is significantly stronger in the ability to prevent cross permeation of vanadium ions than the commercial Nafion115 membrane. In addition, the vanadium ion permeability of the sulfonated polyimide membrane of hydrogen bond self-crosslinking type calculated in this example was 4.40 × 10-7cm2Min, comparative commercial Nafion115 membrane (13.59X 10)-7cm2/min) by an order of magnitude. The hydrogen bond self-crosslinking sulfonated polyimide film has low vanadium ion permeability and is beneficial to improving the coulombic efficiency and the capacity retention capacity of the all-vanadium redox flow battery.
Example 2:
a hydrogen bond self-crosslinking sulfonated polyimide membrane with the thickness of 40 mu m is prepared from a non-amino-terminated sulfonated polyimide high molecular polymer and an amino-terminated sulfonated polyimide high molecular polymer according to the mass ratio of 1.0: 1.5, cross-linking by hydrogen bonds.
The preparation method of the hydrogen bond self-crosslinking sulfonated polyimide membrane comprises the following steps:
(1) under the protection of argon, 3.0mmol of 2,2' -disulfonic acid benzidine, 55.0mL of m-methylphenol and 2.0mL of triethylamine are put into a 250mL three-neck round-bottom flask with a serpentine condenser tube and stirred until solid is dissolved; then adding 3.0mmol of 4,4' -diaminodiphenyl ether, and stirring until the solid is dissolved; finally, 6.0mmol of 1,4,5, 8-naphthalene tetracarboxylic dianhydride and 12.0mmol of benzoic acid are added, the stirring temperature is increased to 75 ℃, the reaction is carried out for 5.0h at the temperature, the temperature is increased to 170 ℃, and the reaction is carried out for 24 h; cooling the reaction system to below 90 ℃, adding 7.7mL of m-methylphenol, stirring the whole reaction process, when the temperature of the reaction system is reduced to 50 ℃, pouring the viscous solution obtained after the reaction into 240mL of acetone serving as a precipitator (the volume ratio of the precipitator to the viscous solution is 3.7: 1.0), generating a precipitation product, filtering, washing the obtained solid with acetone for 3 times, and then drying in vacuum at 80 ℃ for 24 hours to obtain the non-amino-terminated sulfonated polyimide high molecular polymer;
(2) the preparation process of the amino-terminated sulfonated polyimide high-molecular polymer is consistent with the step (1); but the adding amount of the 4,4' -diaminodiphenyl ether is 3.8mmol, and the adding amount of the benzoic acid is 12.8 mmol;
(3) mixing the non-amino-terminated sulfonated polyimide high molecular polymer and the amino-terminated sulfonated polyimide high molecular polymer prepared in the steps (1) and (2) according to the weight ratio of 1.0: dissolving the mixture in dimethyl sulfoxide according to the mass ratio of 1.5 to prepare a high molecular polymer solution with the concentration of 0.09g/mL, and stirring the polymer solution for 20 hours until the polymer solution is uniform; finally, the polymer solution is cast into a film on a clean, smooth and dry glass plate, the thickness of the film is controlled to be 40 microns, the film is dried for 30 hours at 65 ℃, the membrane is peeled off from the glass plate and is placed into 1.5mol/L sulfuric acid aqueous solution to be soaked for 28 hours, then the membrane is taken out, and the membrane is repeatedly washed for 3 times by deionized water, so that the hydrogen bond self-crosslinking sulfonated polyimide film in the embodiment is prepared.
The physical and chemical properties of the hydrogen bond self-crosslinking sulfonated polyimide membrane obtained in this example are shown in table 2.
Table 2: physical and chemical properties of the hydrogen bond self-crosslinking sulfonated polyimide film prepared in example 2
As can be seen from table 2, the water absorption rate, swelling ratio and ion exchange capacity of the hydrogen bond self-crosslinking sulfonated polyimide membrane prepared in this example were lower than those of the separator prepared in example 1, because the number of hydrogen bonds formed was increased due to the increase in the proportion of the amino-terminated sulfonated polyimide high polymer, thereby decreasing the number of hydrophilic sulfonic acid functional groups in the separator. In addition, the proton conductivity of the separator prepared in example 2 was also lower than that of the separator prepared in example 1 due to the decrease in the amount of sulfonic acid groups. In addition, the proton selectivity of the hydrogen bond self-crosslinking sulfonated polyimide membrane is lower than that of the membrane prepared in example 1, but the proton selectivity of the membrane is still higher than that of the commercial Nafion115 membrane. However, more hydrogen bonds are formed in the separator prepared in example 2, causing the molecular chains of the separator to be more densely packed, so that the vanadium ion permeability of the membrane is further reduced.
Example 3:
a hydrogen bond self-crosslinking sulfonated polyimide membrane with the thickness of 55 mu m is prepared from a non-amino-terminated sulfonated polyimide high molecular polymer and an amino-terminated sulfonated polyimide high molecular polymer according to the mass ratio of 1.0: 0.5, cross-linking by hydrogen bonds.
The preparation method of the hydrogen bond self-crosslinking sulfonated polyimide membrane comprises the following steps:
(1) under the protection of argon, 8.0mmol of 2,2' -disulfonic acid benzidine, 110.0mL of m-methylphenol and 5.2mL of triethylamine are put into a 500mL three-neck round-bottom flask with a serpentine condenser tube and stirred until solid is dissolved; then 8.0mmol of 4,4' -diaminodiphenyl ether is added, and the mixture is stirred until the solid is dissolved; finally, 16.0mmol of 1,4,5, 8-naphthalene tetracarboxylic dianhydride and 32.0mmol of benzoic acid are added, the stirring temperature is increased to 90 ℃, the reaction is carried out for 5.5h at the temperature, the temperature is increased to 190 ℃, and the reaction is carried out for 28 h; cooling the reaction system to below 90 ℃, adding 20.0mL of m-methylphenol, stirring the whole reaction process, when the temperature of the reaction system is reduced to 50 ℃, pouring the viscous solution obtained after the reaction into 600mL of precipitator isopropanol (the volume ratio of the precipitator to the viscous solution is 4.6: 1.0), generating a precipitate product, filtering, washing the obtained solid with ethanol for 4 times, and then carrying out vacuum drying at 100 ℃ for 28 hours to obtain the non-amino-terminated sulfonated polyimide high molecular polymer;
(2) the preparation process of the amino-terminated sulfonated polyimide high molecular polymer is consistent with the step (1), but the adding amount of the 4,4' -diaminodiphenyl ether is 10mmol, and the adding amount of the benzoic acid is 34.0 mmol;
(3) mixing the non-amino-terminated sulfonated polyimide high molecular polymer and the amino-terminated sulfonated polyimide high molecular polymer prepared in the steps (1) and (2) according to the weight ratio of 1.0: dissolving the mixture in N-methyl pyrrolidone in a mass ratio of 0.5 to prepare a high molecular polymer solution with the concentration of 0.08g/mL, and stirring the polymer solution for 34h until the polymer solution is uniform; finally, the polymer solution is cast into a film on a clean, smooth and dry glass plate, the thickness of the film is controlled to be 55 microns, the film is dried for 40 hours at the temperature of 75 ℃, the diaphragm is stripped from the glass plate and then is placed into a 2.5mol/L sulfuric acid aqueous solution to be soaked for 30 hours, then the diaphragm is taken out, and the diaphragm is repeatedly washed for 3 times by deionized water, so that the hydrogen bond self-crosslinking sulfonated polyimide film in the embodiment is prepared.
The ion exchange capacity of the hydrogen bond self-crosslinking sulfonated polyimide membrane prepared in the embodiment is 2.10meq/g, which is higher than that of a commercial Nafion115 membrane, and the membrane is proved to have a large number of ion exchange groups capable of transferring protons. In addition, since the amount of the amino-terminated sulfonated polyimide high molecular polymer was decreased and the number of consumed sulfonic acid groups was decreased, the proton conductivity (3.12 × 10) of the separator prepared in example 3 was decreased-2S/cm) was superior to the separators prepared in examples 1 and 2. However, the water absorption and swelling ratio of the composite membrane were 28.2% and 25.1%, respectively, and the reduction of hydrogen bonds resulted in a slight decrease in the dimensional stability of the separator.
Example 4:
a hydrogen bond self-crosslinking sulfonated polyimide membrane with the thickness of 35 mu m is prepared from a non-amino-terminated sulfonated polyimide high molecular polymer and an amino-terminated sulfonated polyimide high molecular polymer according to the mass ratio of 1.0: 2.5, cross-linking through hydrogen bonds.
The preparation method of the hydrogen bond self-crosslinking sulfonated polyimide membrane comprises the following steps:
(1) under the protection of argon, 1.0mmol of 2,2' -disulfonic acid benzidine, 30.0mL of m-methylphenol and 0.7mL of triethylamine are put into a 100mL three-neck round-bottom flask with a serpentine condenser tube and stirred until solid is dissolved; then adding 1.0mmol of 4,4' -diaminodiphenyl ether, and stirring until the solid is dissolved; finally, 2.0mmol of 1,4,5, 8-naphthalene tetracarboxylic dianhydride and 4.0mmol of benzoic acid are added, the stirring temperature is increased to 75 ℃, the reaction is carried out for 5.0h at the temperature, the temperature is increased to 180 ℃, and the reaction is carried out for 25 h; cooling the reaction system to below 90 ℃, adding 2.7mL of m-methylphenol, stirring the whole reaction process, when the temperature of the reaction system is reduced to 50 ℃, pouring the viscous solution obtained after the reaction into 200mL of precipitator ethanol (the volume ratio of the precipitator to the viscous solution is 6.3: 1.0), generating a precipitate product, filtering, washing the obtained solid with acetone for 2 times, and then drying in vacuum at 85 ℃ for 24 hours to obtain the non-amino-terminated sulfonated polyimide high molecular polymer;
(2) the preparation process of the amino-terminated sulfonated polyimide high molecular polymer is consistent with the step (1), but the adding amount of the 4,4' -diaminodiphenyl ether is 1.25mmol, and the adding amount of the benzoic acid is 4.25 mmol;
(3) mixing the non-amino-terminated sulfonated polyimide high molecular polymer and the amino-terminated sulfonated polyimide high molecular polymer prepared in the steps (1) and (2) according to the weight ratio of 1.0: 2.5 in N, N-dimethylformamide to prepare a high molecular polymer solution with the concentration of 0.06g/mL, and stirring the polymer solution for 16 hours until the polymer solution is uniform; finally, the polymer solution is cast into a film on a clean, smooth and dry glass plate, the thickness of the film is controlled to be 35 microns, the film is dried for 26 hours at the temperature of 60 ℃, the diaphragm is stripped from the glass plate and then is placed into 1.5mol/L sulfuric acid aqueous solution to be soaked for 30 hours, then the diaphragm is taken out, and the diaphragm is repeatedly washed for 3 times by deionized water, so that the hydrogen bond self-crosslinking sulfonated polyimide film in the embodiment is prepared.
The ion exchange capacity of the hydrogen bond self-crosslinking sulfonated polyimide membrane prepared in this example was 1.68 meq/g. In addition, since the amount of the amino terminal type sulfonated polyimide high molecular polymer was increased and the number of hydrogen bonds formed was increased, the proton conductivity of the hydrogen bond self-crosslinking type sulfonated polyimide membrane prepared in example 4 was 2.50 × 10-2S/cm. However, the water absorption and swelling ratio of the composite membrane were 25.7% and 15.8%, respectively, and the increase in the number of hydrogen bonds resulted in the enhancement of the dimensional stability of the separator.
Example 5:
a hydrogen bond self-crosslinking sulfonated polyimide membrane with the thickness of 30 mu m is prepared from a non-amino-terminated sulfonated polyimide high molecular polymer and an amino-terminated sulfonated polyimide high molecular polymer according to the mass ratio of 1.0: 0.75, obtained by hydrogen bond crosslinking.
The preparation method of the hydrogen bond self-crosslinking sulfonated polyimide membrane comprises the following steps:
(1) under the protection of argon, 1.5mmol of 2,2' -disulfonic acid benzidine, 45.0mL of m-methylphenol and 1.1mL of triethylamine are put into a 100mL three-neck round-bottom flask with a serpentine condenser tube and stirred until solid is dissolved; then adding 1.5mmol of 4,4' -diaminodiphenyl ether, and stirring until the solid is dissolved; finally, adding 3.0mmol of 1,4,5, 8-naphthalene tetracarboxylic dianhydride and 6.0mmol of benzoic acid, heating the stirring temperature to 85 ℃, reacting for 5.5h at the temperature, heating to 190 ℃, and reacting for 28 h; cooling the reaction system to below 90 ℃, adding 4.1mL of m-methylphenol, stirring the whole reaction process, when the temperature of the reaction system is reduced to 50 ℃, pouring the viscous solution obtained after the reaction into 300mL of acetone serving as a precipitator (the volume ratio of the precipitator to the viscous solution is 6.0: 1.0), generating a precipitation product, filtering, washing the obtained solid with acetone for 4 times, and then drying in vacuum at 100 ℃ for 20 hours to obtain the non-amino-terminated sulfonated polyimide high molecular polymer;
(2) the preparation process of the amino-terminated sulfonated polyimide high molecular polymer is consistent with the step (1), but the adding amount of the 4,4' -diaminodiphenyl ether is 1.88mmol, and the adding amount of the benzoic acid is 6.38 mmol;
(3) mixing the non-amino-terminated sulfonated polyimide high molecular polymer and the amino-terminated sulfonated polyimide high molecular polymer prepared in the steps (1) and (2) according to the weight ratio of 1.0: dissolving the mixture in N, N-dimethylacetamide according to a mass ratio of 0.75 to prepare a high molecular polymer solution with the concentration of 0.07g/mL, and stirring the polymer solution for 35 hours until the polymer solution is uniform; finally, the polymer solution is cast into a film on a clean, smooth and dry glass plate, the thickness of the film is controlled to be 30 microns, then the film is dried for 30 hours at 65 ℃, the diaphragm is stripped from the glass plate and then placed into a 2.0mol/L sulfuric acid aqueous solution to be soaked for 28 hours, then the diaphragm is taken out, and the diaphragm is repeatedly washed for 3 times by deionized water, so that the hydrogen bond self-crosslinking sulfonated polyimide film in the embodiment is prepared.
The ion exchange capacity and proton conductivity of the hydrogen bond self-crosslinking sulfonated polyimide membrane prepared in this example were 2.01meq/g and 2.96X 10, respectively-2S/cm, water absorption and swelling ratio were 27.1% and 22.3%, respectively.
Example 6:
a hydrogen bond self-crosslinking sulfonated polyimide membrane with the thickness of 60 mu m is prepared from a non-amino-terminated sulfonated polyimide high molecular polymer and an amino-terminated sulfonated polyimide high molecular polymer according to the mass ratio of 1.0: 3.0, obtained by hydrogen bond crosslinking.
The preparation method of the hydrogen bond self-crosslinking sulfonated polyimide membrane comprises the following steps:
(1) under the protection of argon, 5.0mmol of 2,2' -disulfonic acid benzidine, 150.0mL of m-methylphenol and 3.3mL of triethylamine are put into a 500mL three-neck round-bottom flask with a serpentine condenser tube and stirred until solid is dissolved; then adding 5.0mmol of 4,4' -diaminodiphenyl ether, and stirring until the solid is dissolved; finally, adding 10.0mmol of 1,4,5, 8-naphthalene tetracarboxylic dianhydride and 20.0mmol of benzoic acid, heating the stirring temperature to 100 ℃, reacting for 3.5h at the temperature, heating to 180 ℃, and reacting for 30 h; cooling the reaction system to below 90 ℃, adding 12.7mL of m-methylphenol, stirring the whole reaction process, when the temperature of the reaction system is reduced to 50 ℃, pouring the viscous solution obtained after the reaction into 400mL of precipitator isopropanol (the volume ratio of the precipitator to the viscous solution is 2.5: 1.0), generating a precipitate product, filtering, washing the obtained solid with acetone for 3 times, and then carrying out vacuum drying at 110 ℃ for 26 hours to obtain the non-amino-terminated sulfonated polyimide high molecular polymer;
(2) the preparation process of the amino-terminated sulfonated polyimide high molecular polymer is consistent with the step (1), but the adding amount of the 4,4' -diaminodiphenyl ether is 6.25mmol, and the adding amount of the benzoic acid is 21.25 mmol;
(3) mixing the non-amino-terminated sulfonated polyimide high molecular polymer and the amino-terminated sulfonated polyimide high molecular polymer prepared in the steps (1) and (2) according to the weight ratio of 1.0: 3.0 mass ratio is dissolved in m-methylphenol to prepare a high molecular polymer solution with the concentration of 0.08g/mL, and the polymer solution is stirred for 40 hours until the solution is uniform; finally, the polymer solution is cast into a film on a clean, smooth and dry glass plate, the thickness of the film is controlled to be 60 microns, the film is dried for 48 hours at 90 ℃, the diaphragm is stripped from the glass plate and then is placed into a 2.5mol/L sulfuric acid aqueous solution to be soaked for 30 hours, then the diaphragm is taken out, and the diaphragm is repeatedly washed for 3 times by deionized water, so that the hydrogen bond self-crosslinking sulfonated polyimide film in the embodiment is prepared.
The ion exchange capacity and proton conductivity of the hydrogen bond self-crosslinking sulfonated polyimide membrane prepared in this example were 1.63meq/g and 2.47X 10, respectively-2S/cm. Because the diaphragm contains a large amount of amino-terminated sulfonated polyimide high molecular polymers, a large amount of hydrogen bonds are formed to help the diaphragm to obtain low water absorption rate (24.5%) and swelling rate (14.7%), and the diaphragm has high dimensional stability.
Example 7:
an application of a hydrogen bond self-crosslinking sulfonated polyimide membrane in the field of all-vanadium flow batteries is provided, wherein the all-vanadium flow batteries utilize a copper foil current collector, a conductive plastic bipolar plate, an activated graphite felt and a diaphragm (the hydrogen bond self-crosslinking sulfonated polyimide membrane prepared in example 1 has an effective membrane area of 30.0cm2) A liquid storage tank, a magnetic pump and the like.
To further demonstrate that the hydrogen bond self-crosslinking sulfonated polyimide membranes prepared in the examples can be applied to all-vanadium flow batteries, the membranes prepared in the examples were applied to all-vanadium flow batteries for testing and performance comparison with all-vanadium flow batteries using commercial Nafion115 membranes. 1.7mol/LVO is respectively put into the positive and negative liquid storage tanks3.5++4.6mol/L sulfuric acid (V)3+：VO2+1: 1) 60.0mL of solution was pumped into the cell via a magnetic pump and circulated between the cell interior and the reservoir. Performing constant-current charge and discharge test on the assembled battery by using a high-precision battery detection system (the current density is 100-20 mA/cm)2) The voltage range is 0.7-1.7V.
As can be seen from FIG. 6, the hydrogen bond self-crosslinking sulfonated polyimide membrane prepared in example 1 has a low vanadium ion permeability, so that the current density is 100-20 mA/cm2Next, the coulombic efficiency of all vanadium flow batteries using the separator prepared in example 1 was higher than that of batteries using commercial Nafion115 membrane. In addition, since the charge and discharge time of the battery is short at a high current density,only minor vanadium penetration between the two pole liquids occurs and therefore the coulombic efficiency of the cell increases with increasing current density. The all-vanadium redox flow battery is used as an electric energy storage system, and the energy efficiency is an important index of the battery. The all-vanadium redox flow battery assembled by using the diaphragm prepared in the embodiment 1 has a current density of 100-20 mA/cm2Also, the energy efficiency was higher than that of the battery using Nafion115 membrane, which is attributable to the high proton selectivity of the hydrogen bond self-crosslinking type sulfonated polyimide membrane.
Claims (10)
1. A hydrogen bond self-crosslinking sulfonated polyimide membrane is characterized by comprising a non-amino-terminated sulfonated polyimide high molecular polymer and an amino-terminated sulfonated polyimide high molecular polymer, wherein the non-amino-terminated sulfonated polyimide high molecular polymer and the amino-terminated sulfonated polyimide high molecular polymer are crosslinked through hydrogen bonds, and the mass ratio of the non-amino-terminated sulfonated polyimide high molecular polymer to the amino-terminated sulfonated polyimide high molecular polymer is 1: 0.25 to 4.
2. The hydrogen bond self-crosslinking sulfonated polyimide membrane according to claim 1, wherein the non-amino-terminated sulfonated polyimide high molecular polymer and the amino-terminated sulfonated polyimide high molecular polymer are randomly crosslinked by a hydrogen bond.
3. The hydrogen bond self-crosslinking sulfonated polyimide film according to claim 1 or 2, wherein the thickness of the hydrogen bond self-crosslinking sulfonated polyimide film is 30 to 65 μm.
4. A method for preparing the hydrogen bond self-crosslinking sulfonated polyimide membrane according to any one of claims 1 to 3, comprising the steps of:
(1) preparing non-amino-terminated sulfonated polyimide high molecular polymer and amino-terminated sulfonated polyimide high molecular polymer by a high-temperature polycondensation method;
(2) dissolving the non-amino-terminated sulfonated polyimide high molecular polymer prepared in the step (1) and the amino-terminated sulfonated polyimide high molecular polymer in an organic solvent to prepare a high molecular polymer solution, mixing and stirring uniformly, casting to form a film, and drying, soaking and washing to prepare the hydrogen bond self-crosslinking sulfonated polyimide film.
5. The method according to claim 4, wherein in the step (1), the high-temperature polycondensation is performed by performing dehydration polycondensation reaction on a diamine monomer and a dianhydride monomer, and the diamine monomer and the dianhydride monomer are the same when the non-amino-terminated sulfonated polyimide high molecular polymer and the amino-terminated sulfonated polyimide high molecular polymer are prepared.
6. The method according to claim 5, wherein the diamine monomer is 2,2 '-disulfonic acid benzidine and 4,4' -diaminodiphenyl ether, and the dianhydride monomer is 1,4,5, 8-naphthalene tetracarboxylic dianhydride;
the specific process of the dehydration polycondensation reaction comprises the following steps: (a) in nitrogen or argon, mixing and stirring 2,2 '-disulfonic acid benzidine, m-methylphenol and triethylamine for dissolving, adding 4,4' -diaminodiphenyl ether solid for dissolving, adding 1,4,5, 8-naphthalene tetracarboxylic dianhydride and benzoic acid, heating to 70-100 ℃, reacting for 2-6 h, heating to 160-200 ℃, and reacting for 10-30 h; (b) and (2) cooling the reaction system to below 90 ℃, adding a diluent, continuously stirring, when the temperature of the reaction system is reduced to 50 ℃, pouring the viscous solution obtained after the reaction into a precipitator to generate a precipitation product, filtering, washing the obtained solid with a detergent for 3-5 times, and drying in vacuum at 60-120 ℃ for 10-30 hours to obtain the sulfonated polyimide high molecular polymer.
7. The method according to claim 6, wherein in the step (a), the molar ratio of 1,4,5, 8-naphthalene tetracarboxylic dianhydride, 2 '-disulfonic acid benzidine, 4' -diaminodiphenyl ether, and benzoic acid is (1.0 to 16.0): (0.5-8.0): (0.6-10.0): (2.1-34.0); the volume ratio of the m-methylphenol to the triethylamine is (7.0-110.0): (0.16-5.2); in the step (b), the diluent is m-methylphenol, the precipitant is any one of acetone, methanol, ethanol or isopropanol, and the detergent is any one of acetone, methanol, ethanol or isopropanol; the volume ratio of the m-methylphenol and the triethylamine serving as the diluents is (1.2-20.0): (0.16-5.2); the volume ratio of the precipitant to the viscous solution is (1.0-10.0): 1.0.
8. the method according to claim 7, wherein the molar ratio of benzidine 2,2 '-disulfonate, 4' -diaminodiphenyl ether and 1,4,5, 8-naphthalene tetracarboxylic dianhydride is 1.0: 1.0: 2.0; when the amino-terminated sulfonated polyimide high molecular polymer is prepared, the molar ratio of 2,2 '-disulfonic acid benzidine, 4' -diaminodiphenyl ether and 1,4,5, 8-naphthalene tetracarboxylic dianhydride is 1.0: 1.25: 2.0.
9. the production method according to any one of claims 4 to 7, wherein in the step (2), the organic solvent is any one of m-methylphenol, dimethyl sulfoxide, N-methylpyrrolidone, N-dimethylformamide, or N, N-dimethylacetamide; the concentration of the high molecular polymer solution is 0.05-0.10 g/mL; the time for mixing and stirring uniformly is 12-48 h, the temperature for drying the formed film is 50-100 ℃, the drying time is 20-60 h, the soaking is carried out for 20-36 h by using a sulfuric acid aqueous solution with the concentration of 1.0-3.0 mol/L, and the washing is carried out for 3-5 times by using deionized water.
10. Application of the hydrogen bond self-crosslinking sulfonated polyimide membrane according to any one of claims 1 to 3 or the hydrogen bond self-crosslinking sulfonated polyimide membrane prepared by the preparation method according to any one of claims 4 to 9 in the field of all-vanadium flow batteries.
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